CN103834233B - Water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion - Google Patents
Water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion Download PDFInfo
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- CN103834233B CN103834233B CN201210488743.9A CN201210488743A CN103834233B CN 103834233 B CN103834233 B CN 103834233B CN 201210488743 A CN201210488743 A CN 201210488743A CN 103834233 B CN103834233 B CN 103834233B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 86
- 239000000839 emulsion Substances 0.000 title claims abstract description 71
- 239000011258 core-shell material Substances 0.000 title claims abstract description 68
- 229920001577 copolymer Polymers 0.000 title claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 239000003973 paint Substances 0.000 title claims abstract description 34
- 239000000049 pigment Substances 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 239000013543 active substance Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000006184 cosolvent Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 19
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 239000002585 base Substances 0.000 claims description 7
- 239000008267 milk Substances 0.000 claims description 7
- 210000004080 milk Anatomy 0.000 claims description 7
- 235000013336 milk Nutrition 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical group NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 6
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229940005605 valeric acid Drugs 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 4
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004159 Potassium persulphate Substances 0.000 claims description 3
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
- COBPKKZHLDDMTB-UHFFFAOYSA-N 2-[2-(2-butoxyethoxy)ethoxy]ethanol Chemical compound CCCCOCCOCCOCCO COBPKKZHLDDMTB-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 229940051250 hexylene glycol Drugs 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005304 joining Methods 0.000 claims description 2
- 229940110337 pigment blue 1 Drugs 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- WPPDXAHGCGPUPK-UHFFFAOYSA-N red 2 Chemical compound C1=CC=CC=C1C(C1=CC=CC=C11)=C(C=2C=3C4=CC=C5C6=CC=C7C8=C(C=9C=CC=CC=9)C9=CC=CC=C9C(C=9C=CC=CC=9)=C8C8=CC=C(C6=C87)C(C=35)=CC=2)C4=C1C1=CC=CC=C1 WPPDXAHGCGPUPK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 239000007921 spray Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000003892 spreading Methods 0.000 abstract description 3
- 230000007480 spreading Effects 0.000 abstract description 3
- 238000009736 wetting Methods 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 57
- 239000000243 solution Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 2
- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- -1 polydimethylsiloxane Polymers 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Cc1ccc(C)cc1 Chemical compound Cc1ccc(C)cc1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 241000011547 Plebejus idas Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920001427 mPEG Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
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Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The present invention relates to a kind of water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion, its weight part composition comprises: core-shell structure copolymer amphiphilic polymers microballoon emulsion 5 ~ 40 parts, water-based pigment colour paste 5 ~ 40 parts, organic cosolvent 1 ~ 30 part, bulk solvent 20 ~ 60 parts, 0.5 ~ 2 part, tensio-active agent.Water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion, effective wetting and spreading improving aqueous pigment ink spray ink Printing in common paper, and realize the low temperature rapid drying of ink for ink-jet print at substrate surface, and good attachment fastness after film forming, the spray ink Printing that can realize in common paper goes out good image effect, and heating unit need not be increased on a printer or print image is carried out to the aftertreatment of the mode such as heat, there is higher market using value.
Description
Technical field
The present invention relates to a kind of water-based paint ink for ink-jet print, particularly a kind of water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion.
Background technology
When aqueous pigment ink is applied to the spray ink Printing of common paper, easily there is the black phenomenon of heap, and drying slowly, the defect such as not water-fast.Solution conventional at present heats to print media printing while, namely adds heating unit on a printer, allowing print media have higher temperature when printing, obviously can improve the quality of printing.But this changes the original structure of printer, and cost also can improve greatly.
Traditional polymer emulsion as film-forming resin, can strengthen the adhesion property of ink at substrate surface in ink for ink-jet print.In water-based system, the bulk solvent of polymer emulsion is water, and the stable existence in order to ensure in ink system and in ink passage, and be unlikely to blocking ink passage and shower nozzle, the film-forming temperature of polymer emulsion is relatively high, rate of drying is lower, the heap ink phenomenon still needing the aftertreatment of the modes such as heating to solve may to occur.
In order to make aqueous pigment ink print good effect in common paper, and possess the performance of low temperature rapid drying film forming, key is to improve from ink self-view, comprises the synthesis improvement of the aspects such as solvent, tensio-active agent, resin emulsion.
Summary of the invention
The object of this invention is to provide a kind of water-based paint ink for ink-jet print, this ink comprises core-shell structure copolymer amphiphilic polymers microballoon emulsion, can realize in the wetting and spreading of substrate surface, low temperature rapid drying, and attachment fastness good after film forming.
For achieving the above object, the present invention takes following technical scheme:
A kind of water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion, its weight percent consists of: core-shell structure copolymer amphiphilic polymers microballoon emulsion 5 ~ 40%, water-based pigment colour paste 5 ~ 40%, organic cosolvent 1 ~ 30%, bulk solvent 20 ~ 60%, tensio-active agent 0.5 ~ 2%.
Described bulk solvent is water, is preferably deionized water.
The water-based paint aqueous solution of described water-based pigment colour paste to be mass concentration be 10 ~ 15wt%; Wherein, water-based paint comprises C.I. Pigment black 7, C.I. Pigment black 11, C.I. pigment blue 1, C.I. pigment Blue 15, C.I. pigment Blue 15: 3, C.I. pigment Blue 15: 4, C.I. pigment Blue 15: 6, C.I. pigment yellow 34, C.I. Pigment Yellow 73 55, C.I. Pigment Yellow 73 74, C.I. Pigment Yellow 73 100, C.I. Pigment red 2, C.I. pigment red 38, C.I. Pigment Red 92, C.I. Pigment red 108, and C.I. pigment red 122.
Described organic cosolvent is ethanol, Virahol, propyl alcohol, isopropylcarbinol, sec-butyl alcohol, glyceryl ether, ethylene glycol, Diethylene Glycol, glycerol, propylene glycol monomethyl ether, butyl glycol ether, triethylene glycol butyl ether, N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), the one in 1,5-PD and hexylene glycol etc. or two or more.
One or more mainly in nonionic surface active agent of described tensio-active agent.Tensio-active agent is polyether-modified polydimethylsiloxane and/or modified polyorganosiloxane interpolymer solution, as Dynol604, Surfynol104E, Surfynol104, Surfynol465; Polyether-modified polydimethylsiloxane: BYK-345, BYK-346, BYK-347, BYK-348, BYK-349; Modified polyorganosiloxane interpolymer solution: BYK-020, BYK-021, BYK-022, BYK-023, BYK-024, BYK-025, BYK-028.These tensio-active agents may be used alone, can also be used in combination.
Add a kind of core-shell structure copolymer amphiphilic polymers microballoon emulsion in the present invention, can be used as the binder component of ink for ink-jet print.Core-shell structure copolymer amphiphilic polymers microballoon emulsion in the present invention have employed the present inventor, and to be documented in application number be technology in the Chinese patent application of 201010292217.6.Wherein, core-shell structure copolymer amphiphilic polymers obtains the amphiphilic block polymers with certain polymerization degree by controllable free-radical copolymerization.Amphiphilic polymers forms stable, that size distribution is narrower milk sap by micelle formation in water.By introducing linking agent, obtain a kind of emulsion system possessing self-crosslinking characteristic of cured at room temperature.Emulsion self is deposited stable, and dry under room temperature after film, micella breaks, and polymkeric substance and small molecules linking agent react, and form tough and tensile and transparent crosslinked film.
Core-shell structure copolymer amphiphilic polymers microballoon emulsion is close to transparent, monodispersed milk sap, and solid content is 10 ~ 20wt%, and wherein the diameter of core-shell structure copolymer amphiphilic polymers microballoon is between 50 ~ 300nm.Disperseed to be formed in water by core-shell structure copolymer amphiphilic polymers, micella inside is containing the group such as functional carboxyl groups, carbonyl.The linking agent preparing the employing of core-shell structure copolymer amphiphilic polymers microballoon emulsion is adipic dihydrazide.
Wherein, core-shell structure copolymer amphiphilic polymers is amphiphilic block polymers, and be a kind of compound containing trithiocarbonic acid ester structure, its chemical structure is as follows:
Wherein, R
1for:
R
2for: CH
3, H;
M is: Na, K, (CH
3)
4n, (C
2h
5)
4n;
M
1monomer is vinylformic acid, methacrylic acid, acrylamide, N-V-Pyrol RC or their mixture;
M
2monomer is vinylbenzene, methyl acrylate, ethyl propenoate, butyl acrylate, isopropyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, isopropyl methacrylate, diacetone-acryloamide(DAA), vinyl cyanide, glycidyl methacrylate or their mixture;
The numerical value of number of repeat unit x is 5 ~ 20; The numerical value of y is 0 ~ 50.The numerical value of number of repeat unit x is preferably 5 ~ 10; The numerical value of y is preferably 5 ~ 20.
Core-shell structure copolymer amphiphilic polymers is that the structure of amphiphilic block polymers can be preferably:
Core-shell structure copolymer amphiphilic polymers has narrow molecular weight distribution, and Mw/Mn is less than 1.30.
Core-shell structure copolymer amphiphilic polymers is by vinylformic acid, poly-(ethylene glycol) methyl ether first acryloyl acid, butyl acrylate, the macromole amphiphilic block polymers that diacetone-acryloamide(DAA) monomer polymerization obtains.
Utilize emulsifier-free emulsion polymerization single stage method to prepare the core-shell structure copolymer amphiphilic polymers microballoon of surface containing hydrophilic radical, hydrophilic radical is in top layer and and with chemical bonds between emulsion particle, Stability Analysis of Structures, forms pure.Meanwhile, by regulating the consumption of reactive emulsifier and polymerization single polymerization monomer can control the size of microballoon and the density of hydrophilic radical easily, thus the character of emulsion particle is changed.In addition, the core-shell polymer microsphere obtained has self-emulsifying properties, and under the condition of not used additives, pressed powder can stably be dispersed in water again.
The preparation method of nuclear-structure polymer shell microballoon, step is as follows:
(1) joining in the water of 10 ~ 100 weight parts by the core-shell structure copolymer amphiphilic polymers of 1 weight part, the initiator of 0.1 ~ 1 weight part, is 7 ~ 7.5 by adjusting PH with base value, generates solution; Initiator is Potassium Persulphate, ammonium persulphate or azo dinitrile valeric acid, preferred azo dinitrile valeric acid; Alkali is sodium hydroxide, potassium hydroxide, lithium hydroxide, Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide.
(2) monomer of 10 ~ 50 weight parts is joined in step (1) gained solution, stir 2 hours under nitrogen protection; Then be warming up to 60 ~ 80 DEG C, stirring reaction 5 ~ 10 hours, obtains the true emulsion of nuclear-structure polymer shell microballoon; Monomer is vinylbenzene, methyl acrylate, ethyl propenoate, butyl acrylate, isopropyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, isopropyl methacrylate, diacetone-acryloamide(DAA), vinyl cyanide, glycidyl methacrylate or their mixture.
(3) linking agent of 1 ~ 3 weight part is joined in above-mentioned milk sap, mixing and stirring, obtain a kind of emulsion system possessing self-crosslinking characteristic of cured at room temperature.Linking agent is adipic dihydrazide.
Spray-drying process, centrifugal or freeze-drying is adopted to prepare the pressed powder of nuclear-structure polymer shell microballoon the true emulsion of the nuclear-structure polymer shell microballoon of gained.The pressed powder made can also become stable emulsion by redispersion in water.
The nuclear-shell emulsion that aforesaid method obtains is containing low-molecular-weight core-shell structure copolymer amphiphilic polymers (according to molecular weight determination), core-shell structure copolymer amphiphilic polymers participates in letex polymerization and becomes a part for emulsion particle, hydrophilic carboxylate units is then in the surface of emulsion particle, plays the effect of stable emulsion.
In core-shell structure copolymer amphiphilic polymers microballoon emulsion in the present invention, the second-order transition temperature of soft section is lower, makes emulsion at room temperature form uniform film.In the process of drying, the micella in emulsion breaks, and polymer molecule linearly state exists, and the carbonyl in molecular chain and linking agent react and form bonding, obtain crosslinked film.Crosslinked film is in water and ethanol, all cannot dissolve in acetone and other organic solvent.
The present invention is on the basis of the large quantity research of Structure and Properties to aqueous pigment ink and polymer microballoon emulsion, by aqueous pigment ink formula system will be used for containing core-shell structure copolymer amphiphilic polymers microballoon emulsion, play the double effects of tensio-active agent and film-forming resin simultaneously, thus effectively improve the wetting and spreading of aqueous pigment ink spray ink Printing in common paper, and realize the low temperature rapid drying of ink for ink-jet print at substrate surface, and good attachment fastness after film forming, there is higher market using value.
Advantage of the present invention:
(1) the core-shell structure copolymer amphiphilic polymers microballoon emulsion described in and between other component of aqueous pigment ink matching good, deposit in process and not easily produce granular precipitate, guarantee system is steady in a long-term.
(2) the water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion, by spray ink Printing on base material, can at room temperature rapid drying film forming, there is good water-fast and solvent resistance.
(3) the water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion, the spray ink Printing that can realize in common paper goes out good image effect, and need not increase heating unit on a printer or print image be carried out to the aftertreatment of the mode such as heat.
Below by the drawings and specific embodiments, the present invention will be further described, but and do not mean that limiting the scope of the invention.
Accompanying drawing explanation
Fig. 1-a and Fig. 1-b is respectively the word print quality effect (positive image) of the embodiment of the present invention 1 ink and other inks.
Fig. 2-a and Fig. 2-b is respectively the word print quality effect (negative) of the embodiment of the present invention 1 ink and other inks.
Embodiment
Embodiment 1:
(1) preparation of core-shell structure copolymer amphiphilic polymers microballoon emulsion (a): the chemical structural formula of the core-shell structure copolymer amphiphilic polymers selected is as follows:
By the above-mentioned core-shell structure copolymer amphiphilic polymers of 1 weight part, the Potassium Persulphate of 0.1 weight part joins in the water of 10 weight parts, is 7.5 by adjusting PH with base value, generates solution; The methyl acrylate of 10 weight parts is joined in above-mentioned solution, stir 2 hours under nitrogen protection; Then be warming up to 80 DEG C, stirring reaction 5 hours, obtains the true emulsion of nuclear-structure polymer shell microballoon; Joined by the adipic dihydrazide of 2 weight parts in above-mentioned milk sap, mixing and stirring, obtains core-shell structure copolymer amphiphilic polymers microballoon emulsion (a).The solid content of gained emulsion (a) is 20wt%, and the diameter of core-shell structure copolymer amphiphilic polymers microballoon is between 50 ~ 300nm.
(2) preparation of water-based paint ink for ink-jet print: according to the composition of table 1, first add mill base and deionized water, after stirring, slowly add core-shell structure copolymer amphiphilic polymers microballoon emulsion (a), stir 1 hour, add tensio-active agent stir half hour again Deng after dispersion completely, then add organic cosolvent, stir 1 hour.
The composition of table 1 embodiment 1 water-based paint ink for ink-jet print
Component | Content (%, with ink total weight) |
C.I. blue 15:4 dispersible pigment color paste (10wt%) | 30 |
Ethylene glycol | 10 |
Butyl glycol ether | 15 |
Core-shell structure copolymer amphiphilic polymers microballoon emulsion (a) | 10 |
Deionized water | 34 |
BYK-345 | 1 |
Embodiment 2:
(1) preparation of core-shell structure copolymer amphiphilic polymers microballoon emulsion (b): the chemical structural formula that core-shell structure copolymer amphiphilic polymers is selected is as follows:
By the above-mentioned core-shell structure copolymer amphiphilic polymers of 1 weight part, the azo dinitrile valeric acid of 0.5 weight part joins in the water of 25 weight parts, is 7.5 by adjusting PH with base value, generates solution; The methyl methacrylate of 15 weight parts is joined in above-mentioned solution, stir 2 hours under nitrogen protection; Then be warming up to 70 DEG C, stirring reaction 8 hours, obtains the true emulsion of nuclear-structure polymer shell microballoon; Joined by the adipic dihydrazide of 3 weight parts in above-mentioned milk sap, mixing and stirring, obtains core-shell structure copolymer amphiphilic polymers microballoon emulsion (b).The solid content of gained emulsion (b) is 15wt%, and the diameter of core-shell structure copolymer amphiphilic polymers microballoon is between 50 ~ 300nm.
(2) preparation of water-based paint ink for ink-jet print: according to the composition of table 2, making processes is identical with embodiment 1.
The composition of table 2 embodiment 2 water-based paint ink for ink-jet print
Component | Content (%, with ink total weight) |
C.I. red 108 dispersible pigment color pastes (10wt%) | 30 |
Ethanol | 10 |
Glycerol | 5 |
Virahol | 15 |
Core-shell structure copolymer amphiphilic polymers microballoon emulsion (b) | 19 |
Deionized water | 20 |
348 of BYK | 1 |
Embodiment 3:
(1) preparation of core-shell structure copolymer amphiphilic polymers microballoon emulsion (c): the chemical structural formula that core-shell structure copolymer amphiphilic polymers is selected is as follows:
By the above-mentioned core-shell structure copolymer amphiphilic polymers of 1 weight part, the azo dinitrile valeric acid of 1 weight part joins in the water of 100 weight parts, is 7 by adjusting PH with base value, generates solution; The methyl methacrylate of 50 weight parts and butyl methacrylate (weight ratio 1:1) are joined in above-mentioned solution, stirs 2 hours under nitrogen protection; Then be warming up to 60 DEG C, stirring reaction 10 hours, obtains the true emulsion of nuclear-structure polymer shell microballoon; Joined by the adipic dihydrazide of 1 weight part in above-mentioned milk sap, mixing and stirring, obtains core-shell structure copolymer amphiphilic polymers microballoon emulsion (c).The solid content of gained emulsion (c) is 10wt%, and the diameter of core-shell structure copolymer amphiphilic polymers microballoon is between 50 ~ 300nm.
(2) preparation of water-based paint ink for ink-jet print: according to the composition of table 3, making processes is identical with embodiment 1.
The composition of table 3 embodiment 3 water-based paint ink for ink-jet print
Component | Content (%, with ink total weight) |
C.I. red 122 dispersible pigment color pastes (10wt%) | 40 |
Diethylene Glycol | 10 |
Propylene glycol monomethyl ether | 15 |
Core-shell structure copolymer amphiphilic polymers microballoon emulsion (c) | 5 |
Deionized water | 29 |
Surfynol 465 | 1 |
Embodiment 4:
The preparation of water-based paint ink for ink-jet print: according to the composition of table 4, making processes is identical with embodiment 3.
The composition of table 4 embodiment 4 water-based paint ink for ink-jet print
Component | Content (%, with ink total weight) |
C.I. yellow 74 dispersible pigment color pastes (12wt%) | 5 |
Propyl alcohol | 14.5 |
Core-shell structure copolymer amphiphilic polymers microballoon emulsion (c) | 40 |
Deionized water | 40 |
Surfynol 465 | 0.5 |
Embodiment 5:
The preparation of water-based paint ink for ink-jet print: according to the composition of table 5, making processes is identical with embodiment 2.
The composition of table 5 embodiment 5 water-based paint ink for ink-jet print
Component | Content (%, with ink total weight) |
C.I. yellow 100 dispersible pigment color pastes (10wt%) | 15 |
Glyceryl ether | 1 |
Core-shell structure copolymer amphiphilic polymers microballoon emulsion (b) | 22 |
Deionized water | 60 |
BYK-028 | 2 |
Embodiment 6:
The preparation of water-based paint ink for ink-jet print: according to the composition of table 6, making processes is identical with embodiment 1.
The composition of table 6 embodiment 6 water-based paint ink for ink-jet print
Component | Content (%, with ink total weight) |
C.I. black 11 dispersible pigment color pastes (15wt%) | 10 |
1,5-PD | 3 |
Propyl alcohol | 17 |
Core-shell structure copolymer amphiphilic polymers microballoon emulsion (a) | 20 |
Deionized water | 48.5 |
Dynol 604 | 1.5 |
The performance of water-based paint ink for ink-jet print prepared by embodiment 1 ~ 6 is tested, the results are shown in Table 7.
The performance perameter of table 7 embodiment 1 ~ 6 water-based paint ink for ink-jet print
The formula of above-mentioned 6 embodiments, in stable homogeneous, prints fluency, all has good performance in the quick-drying after color character and ink print in common paper and adhesion performance etc.The ink obtain embodiment 1 and other inks (the original-pack ink of Epson desktop printer) print in common paper, and print specimen page seasoning, word print quality effect photo-positive image and negative are as shown in Fig. 1-a, Fig. 1-b, Fig. 2-a and Fig. 2-b.Can be found out by contrast, the quality of the ink printed specimen page in the present embodiment is higher, and ink can rapid drying at substrate surface, without the black phenomenon of heap.
Claims (7)
1. the water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion, it is characterized in that: its weight percent consists of: core-shell structure copolymer amphiphilic polymers microballoon emulsion 5 ~ 40%, water-based pigment colour paste 5 ~ 40%, organic cosolvent 1 ~ 30%, bulk solvent 20 ~ 60%, tensio-active agent 0.5 ~ 2%; Described organic cosolvent is one in ethanol, Virahol, propyl alcohol, isopropylcarbinol, sec-butyl alcohol, glyceryl ether, ethylene glycol, Diethylene Glycol, glycerol, propylene glycol monomethyl ether, butyl glycol ether, triethylene glycol butyl ether, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO), 1,5-PD and hexylene glycol or two or more; Described bulk solvent is water;
Described core-shell structure copolymer amphiphilic polymers microballoon emulsion is disperseed to be formed by core-shell structure copolymer amphiphilic polymers in water, and the chemical structural formula of described core-shell structure copolymer amphiphilic polymers is as follows:
Wherein, R
1for:
R
2for: CH
3, H;
M is: Na, K, (CH
3)
4n, (C
2h
5)
4n;
M
1monomer is vinylformic acid, methacrylic acid, acrylamide, N-V-Pyrol RC or their mixture;
M
2monomer is vinylbenzene, methyl acrylate, ethyl propenoate, butyl acrylate, isopropyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, isopropyl methacrylate, diacetone-acryloamide(DAA), vinyl cyanide, glycidyl methacrylate or their mixture;
The numerical value of number of repeat unit x is 5 ~ 20; The numerical value of y is 0 ~ 50;
The preparation method of described core-shell structure copolymer amphiphilic polymers microballoon emulsion, step is as follows:
(1) joining in the water of 10 ~ 100 weight parts by the core-shell structure copolymer amphiphilic polymers of 1 weight part, the initiator of 0.1 ~ 1 weight part, is 7 ~ 7.5 by adjusting PH with base value, generates solution; Initiator is Potassium Persulphate, ammonium persulphate or azo dinitrile valeric acid; Alkali is sodium hydroxide, potassium hydroxide, lithium hydroxide, Tetramethylammonium hydroxide or tetraethyl ammonium hydroxide;
(2) monomer of 10 ~ 50 weight parts is joined in step (1) gained solution, stir 2 hours under nitrogen protection; Then be warming up to 60 ~ 80 DEG C, stirring reaction 5 ~ 10 hours, obtains the true emulsion of nuclear-structure polymer shell microballoon; Monomer is vinylbenzene, methyl acrylate, ethyl propenoate, butyl acrylate, isopropyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, isopropyl methacrylate, diacetone-acryloamide(DAA), vinyl cyanide, glycidyl methacrylate or their mixture;
(3) join in above-mentioned milk sap by the linking agent of 1 ~ 3 weight part, linking agent is adipic dihydrazide, and mixing and stirring, obtains emulsion system.
2. the water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion according to claim 1, is characterized in that: the chemical structural formula of described core-shell structure copolymer amphiphilic polymers is:
3. the water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion according to claim 2, is characterized in that: described core-shell structure copolymer amphiphilic polymers microballoon emulsion is monodisperse emulsion, and solid content is 10 ~ 20wt%.
4. the water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion according to claim 3, is characterized in that: in described core-shell structure copolymer amphiphilic polymers microballoon emulsion, the diameter of microballoon is 50 ~ 300nm.
5. the water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion according to claim 4, is characterized in that: the mass concentration 10 ~ 15wt% of described water-based pigment colour paste.
6. the water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion according to claim 5, is characterized in that: described water-based paint is C.I. Pigment black 7, C.I. Pigment black 11, C.I. pigment blue 1, C.I. pigment Blue 15, C.I. pigment Blue 15: 3, C.I. pigment Blue 15: 4, C.I. pigment Blue 15: 6, C.I. pigment yellow 34, C.I. Pigment Yellow 73 55, C.I. Pigment Yellow 73 74, C.I. Pigment Yellow 73 100, C.I. Pigment red 2, C.I. pigment red 38, C.I. Pigment Red 92, C.I. Pigment red 108 and/or C.I. pigment red 122.
7. the water-based paint ink for ink-jet print containing core-shell structure copolymer amphiphilic polymers microballoon emulsion according to claim 1, is characterized in that: described tensio-active agent is one or more in nonionic surface active agent.
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